Patent GB-810023-A (GB)
Title: Method of polymerization of olefins and the linear high molecular weight polymers produced thereby
IPC: B65G65/00
Filed: 1955-06-07
Abstract: Catalysts used in polymerizing olefins are formed by contacting a halide (other than a fluoride) of a Group IVa, Va or VIa metal with a metal, alloy, metal hydride, complex metal hydride, or an organo-metallic compound or boron complex thereof, of a metal of Groups Ia or II or of aluminium.  Specified catalyst components are titanium tetrachloride, tetrabromide and tetraiodide; zirconium and vanadium tetrachloride; molybdenum tri- and penta-chlorides; aluminium compounds of formul  R1R11AlR111, wherein R1 and R1 and R11 are hydrocarbon radicals and R111 is hydrocarbon, hydrogen, halogen, or alkoxy; the compounds A[MR1R11XY], wherein A is an alkali metal, M is aluminium or boron and X and Y are hydrocarbon or hydrogen; and organic compounds of magnesium or zinc.  The catalysts may be prepared in the presence of inert solvents and/or the olefins to be polymerized.  Catalyst residues may be subsequently decomposed by treatment with acetone, alcohol or water followed by treatment with acid, e.g. hydrochloric acid in methanol or ether.ALSO:a -Olefins of at least 3 carbon atoms are polymerized with a catalyst produced by contacting a halide (other than a fluoride) of a Group IVa, Va or VIa metal with a metal, alloy, metal hydride or complex thereof, or an organo-metallic compound or complex thereof with boron, of a metal of Groups Ia or II or of aluminium. Olefins specified are a -olefins of formula R-CH=CH2 wherein R is alkyl, cycloalkyl, cycloalkenyl or aryl; or mixtures thereof with one another and/or with ethylene and/or a diolefin. Preferred monomers are propylene, butene-1, pentene-1, hexene-1 and styrene, and in examples 22 and 30 isoprene and 1-vinyl-cyclohexene-4 are also included.  The Group VIa, Va or VIa compound may be titanium tetrachloride, tetrabromide or tetraiodide, zirconium or vanadium tetrachloride, or molybdenum tri- or penta-chloride.  The other catalyst component may be: an aluminium compound of formula R1R11AlR111, wherein R1 and R11 are hydrocarbon radicals and R111 is hydrocarbon, hydrogen, halogen or alkoxy; a compound A[MR1R11XY], wherein A is an alkali metal, M is aliminium or boron and X and Y are hydrocarbon or hydrogen; and organic compounds of magnesium or zinc.  The catalyst components are preferably contacted in the presence of the olefin to be polymerized or in inert solvents and the polymerization may be in the liquid state, e.g. in liquid olefin or in solution.  Solvents disclosed are previously purified diesel oil, petroleum, isooctane, benzene, hexane and heptane.  Catalyst components and/or monomer may be added stepwise or continuously during the polymerization.  The a -olefins are selectively polymerized using the above catalysts and polybutene-1 may be obtained from a mixture of butene-1 and butene-2.  When using aluminium triethyl as a catalyst component some ethylene is formed and copolymerizes. The catalysts may be decomposed and the products purified by treatment with acetone, alcohol or water, followed by treatment with acid, e.g. hydrochloric acid in methanol or ether. The products are mixtures of polymers of different molecular weights and steric configurations and may be separated by specified solvents (if desired after stretching) into oils, rubbery materials and partially and completely crystalline materials.  The polymers are linear, unbranched, head-to-tail materials of which the crystalline products are of high molecular weight and density and may have a spiral chain wherein the asymmetric carbon atoms have the same configuration.  Propylene polymers of M.P.>160 DEG  C. and styrene polymers of M.W. 2,800,000 and M.P.>200 DEG  C. are obtained.  The polymers may be formed into fibres, foils and filaments (which may be cold stretched) or into elastomeric products and compositions. Applications specified are textile fibres, foils, electric cables, insulating material and cable-ropes which float.